Phosphorous-containing, organic polymerisable silanes and silicic acid polycondensates produced therewith

ABSTRACT

The invention relates to compounds of formula (I) (XaRbSi)m[(B) ([O]oP[O]pR′cYd)n]4-a-b (I), where the groups, residues and indices have the following meanings: B=an at least doubly-valent straight chained or branched group with at least one organic polymerisable group and at least three carbon atoms, X=a group which may be cleaved from the silicon atom by hydrolysis, R=optionally substituted alkyl, alkanyl, aryl, alkylaryl or arylalkyl, R′═R, Y═Cl, OH or OR′, R″═H, alkyl or aryl, a=0, 1, 2 or 3, b=0, 1 or 2, a+b together=1, 2 or 3, c=0, 1 or 2, d=0, 1 or 2, c+d together=2, m=at least 1, with the proviso that m is not greater than 1 when a+b=1 or 2, n=at least 1, o=0 or 1 and p=0 or 1. The invention further relates to a series of methods by which the above compounds may be produced.

[0001] The present invention relates to novel molecules, which compriseat least one silane group with possibly hydrolysable radicals, at leastone organically polymerisable group and at least one reactivephosphorous-containing group or phosphorous-containing group thatmodulates the properties of the molecule, respectively. Moreover theinvention relates to hydrolysis and condensation products of thesemolecules, which were produced while using said molecules. And finallythe invention relates to a method for producing the inventive molecules.

[0002] Silicic acid hetero-polycondensates, which can be obtainedthrough the hydrolysis and condensation of silanes with hydrolysablegroups, have been known for a long time (see e.g. DE PS 27 58 414). Suchcondensates can be processed into various products, for example intoprotective layers, coatings, membranes or bulk materials. The underlyingsilanes can also comprise double bonds or other organically reactivegroups, through which they can be polymerized into an organic network(see e.g. DE 40 1.1 044 C2 and DE 44 05 261 A1). Such materials can beused for example in the production of dental materials (see e.g. 41 33494 C2).

[0003] We also know of silane compounds, which have aphosphorous-containing group in the molecule. It has long been knownabout phosphorous-containing materials that they can haveflame-retarding properties. DE 198 32 094 A1 suggests to mix dispersionscomprising at least one water insoluble organo-polymer and awater-dispersible silicon compound with a dispersible phosphorouscompound in order to make the textile materials produced from thedispersions flame-resistant. In a special design the phosphorouscompounds used are such compounds, which additionally carry one siliconatom in the molecule, for example triethoxy silyl ethane phosphoric aciddiethyl ester, which is commercially available. Pursuant to EP 525 573A1 it is supposed to be possible to use phosphorous-group containingorgano-silanes as immuno-regulators. U.S. Pat. No. 4,772,408 suggestsphosphonate silanes as stabilizers for anti-freezes.

[0004] The synthesis of above-mentioned phosphorous-containing silanescan in principle occur via two methods: Either a silane containing anorganic double bond is reacted with a P—H bond of a phosphonate or thelike, or an alkoxy group on the phosphorous is reacted with a halogen.

[0005] It is the object of the present invention to provide novelinorganic-organic resins that are obtained through the hydrolysis andcondensation of silane-containing educts, wherein monomers comprisingphosphorous-containing groups can be or have been condensed into saidresins. The presence of the phosphorous-containing groups shall conveymodified properties to these materials and/or the coatings or bulkmaterials produced thereof either through their chemical functionality(e.g. reaction with complexable groups) or their physical properties(e.g. improved flame resistance, higher polarity). Additionally it isthe object of the invention to provide a novel group of compounds, whichare suited for the production of such resins and which beyond thatenable improved bonding with inorganic and/or organic constituents ofsaid resins.

[0006] Pursuant to the invention compounds are made available thatcontain a hydrolysable silane radical or its hydrolysis products, areactive phosphorous-containing radical or a phosphorous-containingradical, which upon incorporation of the compounds in an inorganicand/or organic network modulates the network's properties, as well as anorganically polymerisable radical.

[0007] All three molecules can be used for property modificationpurposes in accordance with JTB (ISC) 1992, p. 61-72 andPolymer+Materials Research Symposium 1993, Bayreuth, Germany, p. 14-17.The phosphorous-containing molecule part hereby offers the massesproduced with the inventive compounds additional variability, whichleads to special and novel combinations of characteristics.

[0008] With the help of such compounds either the aforementioned resinscan be produced, which in turn can be used to produce organiccross-linked products, or they can be processed directly into organicpolymerizates, which may subsequently be further cross-linked throughthe hydrolysis and possible condensation of the developing groups.

[0009] Accordingly the invention provides compounds of the formula I

(X_(a)R_(b)Si)_(m)[—{B}—([O]_(c)P[O]_(p)R′_(c)Y_(d))_(n)]_(4a-b−I)

[0010] wherein the radicals and indices have the following meaning:

[0011] B is a straight-chained or branched radical with at least oneorganic polymerisable group, which is preferably a C═C double bond, andat least 3, rather 4, and preferably up to 50 carbon atoms, X is aradical that can be cleaved from the silicon atom by hydrolysis,especially hydrogen, halogen and here preferably chlorine, hydroxy,alkoxy with preferably 1 to 4 carbon atoms, acyloxy with preferably 2 to5 carbon atoms, alkylcarbonyl with preferably 2 to 6 carbon atoms,alkoxycarbonyl with preferably 2 to 6 carbon atoms or NR″ and canpossibly have different meanings in a compound of the formula I,

[0012] R is possibly substituted alkyl, alkenyl, aryl, alkylaryl orarylalkyl with preferably 1-6 carbon atoms for open-chained aliphaticgroups and preferably 6 to 12 carbon atoms for cyclo-aliphatic oraromatic groups, wherein the substitution can occur for example withhalogen or amino groups, oxygen-containing and/or sulfur-containingradicals,

[0013] R′ can have the same meaning as R,

[0014] Y is Cl, OH or OR′,

[0015] R″ is hydrogen, alkyl with preferably 14 carbon atoms or arylwith preferably 6-12 carbon atoms,

[0016] a is 0, 1, 2 or 3,

[0017] b is 0, 1 or 2,

[0018] a+b together are 1, 2 or 3,

[0019] c is 0, 1 or 2,

[0020] d is 0, 1 or 2,

[0021] c+d together are 2,

[0022] m is preferably 1, but can also be 2, 3, 4 or possibly even ahigher number, but only when a+b means 3,

[0023] n is preferably 1, but can also be 2, 3, 4 or possibly even ahigher number,

[0024] o is 0 or 1, and

[0025] p is 0 or 1.

[0026] B is a radical with at least 2 bonds (namely at least one to thephosphorous-containing group and at least one to the silane group). Whenm and/or n are greater than 1, several silane- or phosphorous-containingradicals are bound to respectively different atoms (e.g. C atoms) in theradical B, the number of these bonds of B then increases accordingly.When a+b together are 1 or 2, the number of B-containing radicals on thesilicon, which is defined at 4-a-b, becomes 2 or 3.

[0027] This means that the silicon atom is arranged between two or even3 such groups. In such cases, however, according to the definition mshould be equal to 1 (otherwise Formula I would also comprisepoly-condensates). Designs with a+b equal 1 or 2 are possible above allwhen the radical B is not very complex from a steric point of view.

[0028] B itself can contain the or at least one of the organicpolymerisable groups in its main chain (i.e. in the chain that bonds thephosphorous-containing radical and the silane radical); frequently thisgroup or at least one of these groups can be found in a side chain. Theorganic polymerisable group(s) can be selected randomly. They can bee.g. vinyl, allyl, norbornen, glycidyl, acryl or methacryl groups.Preferably B is derived from a substituted or unsubstituted compoundwith acrylate or methacrylate groups. B can comprise a continuous carbonskeleton, the carbon chain(s) (main and/or side chain(s)) however canalso be interrupted by hetero-atoms or groups such as O, S, SO, NH,NHCO, PR, POR, CONHCO, COO, NHCOO or the like. Moreover, B can be boundto the silane radical via such groups. The carbon skeleton can beexclusively aliphatic, with open and/or closed structures. B however canalso comprise one or more aromatic core(s) or condensed systems ortriazine groups or the like, e.g. bisphenol-A structures or the like.Furthermore the groups or structure can be randomly substituted, e.g.with acid, acid amide, ester or amino groups.

[0029] In a preferred design, B comprises at least one acrylate ormethacrylate group. As will be explained in the following in thedescription of possible manufacturing methods for the inventivecompounds, it is particularly preferred—proceeding from oligo- orpoly-acrylates or methacrylates with at least three 3 (meth)acrylgroups—to arrive at compounds in which B represents a radical in whichat least 2 (meth)acrylate groups were reacted with at least onephosphorous-containing molecule and at least one silane molecule or itsprecursor so that the radical B comprises at least 2 fewer(meth)acrylate groups than the oligo- or poly(meth)acrylate, which wasused to produce the inventive compound. Instead however it is alsopossible to proceed from oligo- or polyacrylates or methacrylates, whichcompared to the compounds of the present invention comprise oneadditional (meth)acrylate group if these (meth)acrylates additionallycontain a hydroxy group, via which e.g. an isocyanatosilane can becoupled. Instead of (meth)acrylates of course other organicpolymerisable radicals, e.g. alkylene oxide groups, especially glycideether groups, or vinyl or allyl or norbornen groups are suited as well.Several different such groups in B or its precursor are also possible inprinciple. Particular preferred as structural elements of B are amongother things the trimethylolpropane group, the penta-erythritol groupand the glycerol structure.

[0030] The groups containing the phosphorous can be selected fromphosphates (esters of phosphoric acid H₃PO₂), phosphonates (esters ofphosphonic acid HP(O)(OH)₂), trialkyl esters of the phosphorous acidtautomeric with the phosphonic acid, esters of the phosphinic acidH₂P(O)(OH), trialkyl/arylphosphine oxides and trialkyl/arylphosphines,wherein generally the “acid protons” of the underlying acid, with saidprotons being located on the phosphorous, are replaced by an alkyl groupand the hydroxy groups of the underlying acid by alkoxy groups. Theradical (X_(B)R_(b)Si)_(m)—{B}-hereby preferably exists directly bondedto the phosphorous atom (i.e. o is zero) since the phosphoric acid estergroups tend to cleave in an aqueous medium by hydrolysis so that suchmolecules are less stable at least in a certain environment. Due totheir properties, which will be explained further below, esters of thephosphonic acid and esters of the phosphinic acid are preferred themost.

[0031] Accordingly in the group [O]_(o)P[O]_(p)R′_(c)Y_(d) of Formula Iin preferred designs of the invention o is equal to zero. Similarlypreferred is c equal to 0 or 1, and particularly preferred is c equal 0.In all these designs that are mentioned as being preferred, p ispreferably 1. R′is preferably alkyl or aryl, especially methyl, ethyl,n- or iso-propyl or n-, iso- or t-butyl, and Y is preferably alkoxy oraryloxy, especially methoxy, ethoxy, n- or iso-propoxy or n-, iso- orb-butoxy. Instead the phosphonic acid or phosphinic acid esters can alsoexist in hydrolysed form, i.e. Y can also mean hydroxy.

[0032] The substituents or radical X and R located on the silicon atomcan be selected randomly. In literature about materials containinginorganic-organic silicon atoms, e.g. such that are commerciallyavailable under the term “ORMOCER”®, much has been written about therespective properties, which the respective silane radicals convey tothe condensate or organic polymerized network, so that no detailedexplanations are required in this respect. X signifies hydrolysableradicals. With these groups, which are also called inorganic networkformers, in cooperation with possibly existing organic network formers,namely organic polymerisable groups (in the present case also thegroup(s) [—{B}—([O]₀P[O]_(p)R′_(c)Y_(d))_(n)], physical properties ofthe developing network are adjusted, such as hardness or flexibility,thermal stability, thermal coefficient of expansion. The not organicpolymerisable groups R are described as network modifiers; through theirselection also a series of properties can be influenced.

[0033] The production of the inventive compounds can occur in manydifferent ways.

[0034] A first method starts with compounds II

(X_(a)R_(b)Si)_(m)[—{B¹}]_(4-a-b)  II

[0035] wherein X, R, a, b and m have the meanings as defined in FormulaI and B¹ is a group, which comprises one C═C double bond more than groupB. These compounds are reacted with

H—P[O]_(p)R′_(c)Y_(d)  III,

[0036] wherein R′, Y, c and d can have the aforementioned meanings and pis 1. The hydride reacts with one of the double bonds on the group B¹while forming the group —CHR¹—CR²R³—P[O]_(p)R′_(c)Y_(d), wherein thegroup —CHR¹—CR²R³ is a part of B. This way phosphonic acid esterderivatives and phosphinic acid ester derivates can be produced. Thereaction occurs preferably while adding a radical (e.g. fornon-activated double bonds) or alkaline (e.g. for activated doublebonds) catalyst, e.g. a sodium alcoholate. It is particularlyadvantageous if the double bond of B¹ that is involved in the reactionis part of a Michael system, e.g. part of a (meth)acrylate group. In thecompound III, d can mean for example 2 and Y can be an alkoxy group, orc and d can each mean 1 and R′ can be an alkyl group and Y an alkoxygroup.

[0037] A second method proceeds from compounds IV

(X_(a)R_(b)Si)_(m)[—{B²}]_(4-a-b)  IV,

[0038] wherein X, R, a, b and m have the meanings as defined in FormulaI and B² is a group, which comprises one OH group more than group B.These compounds are reacted in the presence of an alkaline catalyst withPOCl₃, wherein a group (X_(a)R_(b)Si)_(m)[—{B}—]_(4-a-b)O is bound tothe phosphorous atom with simultaneous cleavage of HCl. The remainingchloride atoms are subsequently displaced, possibly through reactionwith suitable alcoholates; both the chloride and alcoholate groups areopen to hydrolysis later on. During this reaction, which leads tophosphoric acid esters, a slightly careless conduction of the reactionwith mixtures of the desired reaction product can easily lead toproducts in which the silane has been added twice so that cleaning stepsmay be required.

[0039] A third method utilizes the reaction of compound IV withphosphorous pentoxide. The product is a corresponding phosphoric acidmono-ester of the formula I, wherein Y is OH, o and p are 1, c is zeroand d is 2.

[0040] A fourth method employs the Arbuzov Reaction. Hereby compounds V

(X_(a)R_(b)Si)_(m)[—{B³}]_(4-a-b)  V,

[0041] wherein B³ is a group deduced from B, which contains anadditional halogen atom, are reacted with phosphorous compounds of theformula VI,

R′_(c)PY_(d)  VI

[0042] wherein R′ and Y have the meanings provided for Formula I and cis 0, 1 or 2, d is 1, 2 or 3 and c+d is 3. If phosphorous compounds VIare used, in which c is equal 0, phosphonic acid esters are obtained. Ifphosphorous compounds VI are used, in which c is equal 1, phosphinicacid esters are produced, and if phosphorous compounds VI are used, inwhich c is equal 2, phosphine oxide compounds are obtained.

[0043] The above-mentioned reaction methods for the production ofcompounds I are of course not exhaustive. For example compounds can beproduced in other ways, wherein additional functional groups areintroduced into the radical B. One example is the reaction of compoundsof the formula III with silanes of the formula IV, which however insteadof a hydroxy group comprise additionally an aldehyde group, andsubsequently with an acid chloride in the presence of a silane:

[0044] [Formulas]

[0045] Such reactions are also possible e.g. with appropriate ketonesinstead of the aldehydes.

[0046] Silanes of the formulas II and IV are known in great numbers.Compounds of the formula II can be produced for example in that a silaneof the general Formula VII

X_(a)R_(b)SiR⁴D  VII

[0047] in which X and R are defined as in Formula I, a+b is 3, R⁴ isalkyl, arylene or alkylene-arylene and D means the group SH, PR⁵H orPOR⁵H with R⁵ being hydrogen, alkyl or aryl, is subjected to an additionreaction with a compound B⁴, which comprises one C═C double bond morethan the Group B¹ in Formula II. In the developing product with theFormula II, B¹ is bound to the silicon atom via a group R⁴D′ with D′equal S, PR⁵ or POR⁶.

[0048] Alternatively, silanes of the Formulas II and IV can be producedin that a silane of the formula

X_(a)R_(b)SiR⁴NCO  VIII

[0049] wherein X, R, a, b and R⁴ have the same meanings as in FormulaVII, is subjected to condensation reaction with a compound B⁵, which isa hydroxy- or amino- or SH-substituted derivative of the Group B¹ inFormula II. In the developing product with the Formula II, B¹ is boundto the silicon atom via a group R⁴D′ with D′ equal NHC(O)O.

[0050] Moreover silanes of the Formulas II and IV can be produced e.g.in that a silane with the Formula IX

X_(a)R_(b)SiH  IX

[0051] wherein X, R, a and B have the same meanings as in Formula VII,is subjected to hydrosilylation reaction with a compound B⁴, whichcomprises one C═C double bond more than the Group B¹ in Formula II.

[0052] Compounds of the Formula IV can be obtained in the same manner,wherein instead of the compounds B⁴ or B⁵ compounds B⁶ are used, whichcompared to the compounds B⁴ and B⁵ contain one hydroxy group (more).

[0053] Examples for such compounds can be found e.g. in DE 41 33 494 A1,DE 43 10 733 A1, DE 44 05 261, DE 44 16 857 A1 or DE 198 32 965 A1.

[0054] For the expert it is evident that the aforementioned productionprocesses, in all of which the phosphorous-containing group is coupledlast to the molecule that is to be produced, can also be reversed, i.e.that first the phosphorous-containing group is bound to thecorresponding derivatives of B and then the silicon-containing group.

[0055] If the compounds of Formula I contain groups X and/or Y in themolecule, they can be subjected to hydrolysis. Since the hydrolysisconditions can deviate for groups Y from those for groups X, especiallywhen X and Y are alkoxy groups, hydrolysis can occur selectively. Alkoxygroups are for example cleaved from the silicon atom in the presence ofwater and possibly a solvent already under mild conditions; they remainon the phosphorous atom. The hydrolysis of alkoxy groups on thephosphorous atom by contrast succeeds specifically in the presence oftrimethyl silyl bromide and methanol as the catalyst. Under more acidicconditions (for example in an aqueous-acidic medium at elevatedtemperatures), the groups can be cleaved from both types of atoms.

[0056] The following shall clarify this:

[0057] 1. Hydrolysis of the phosphonate and alkoxy group

[0058] (reaction)

[0059] 2. Selective hydrolysis of the alkoxy group possible

[0060] (reaction)

[0061] H₂O/Solvent/reduced temperature (mild condition)

[0062] 3. Selective hydrolysis of the phosphonate possible

[0063] (reaction)

[0064] The inventive compounds of the Formula I can be embedded ininorganic networks with Si—O—Si units if they contain hydrolysable orhydrolysed radicals on the silicon atom. Moreover they are supposed tobe able to be embedded in organic polymer structures by means of theradicals B, or such structures are supposed to be able to be built bymeans of the organic polymerisable groups of the radicals B. Inorganiccondensed silicic acid hetero-polycondensates and products that can beobtained through the organic cross-linkage of such condensates are knownin larger numbers. In principle they are produced based on a sol-gelprocess. The condensates can be used in various applications, e.g. asmolding compounds, as paints for coatings and the like.

[0065] If the inventive compounds of the Formula I contain groups X,they can be hydrolysed and condensed in an alkaline or acidicenvironment without already causing a cross-linkage via the organicpolymerisable groups into the developing polymerisate. This way it ispossible to embed them in any random networks, which can consist eitherexclusively of compounds of the Formula I or also of a mixture withother silanes, as we know them from the prior art. Moreover it should bepossible to build an organic network through polymerization of theorganic groups contained in the radical B. This allows these compoundsto be used in a variety of coating, filling, adhesion and sealingcompounds as molded bodies and embedding compounds.

[0066] The present invention accordingly furthermore provides silicicacid polycondensates, which are produced while including silanes of thegeneral Formula X

(X_(a)R_(b)Si)_(m)[—{B⁷}—([O]₀P[O]_(p)R′_(c)Y_(d))_(n)]_(4a-b)  X.

[0067] In the silanes of the Formula X the radicals and indices have thefollowing meaning:

[0068] B⁷ is a straight-chained or branched radical with possibly one ormore organic polymerisable group, preferably a C═C double bond, and atleast 1, preferably 2 to 50 carbon atoms, X is a radical that can becleaved from the silicon atom by hydrolysis, especially hydrogen,halogen and here preferably chlorine, hydroxy, alkoxy with preferably 1to 4 carbon atoms, acyloxy with preferably 2 to 5 carbon atoms,alkylcarbonyl with preferably 2 to 6 carbon atoms, alkoxycarbonyl withpreferably 2 to 6 carbon atoms or NR″ and can possibly have differentmeanings in a compound of the formula I,

[0069] R is possibly substituted alkyl, alkenyl, aryl, alkylaryl orarylalkyl with preferably 1-6 carbon atoms for open-chained aliphaticgroups and preferably 6 to 12 carbon atoms for cyclo-aliphatic oraromatic groups, wherein the substitution can occur for example withhalogen or amino groups,

[0070] R′ can have the same meaning as R,

[0071] Y is Cl, OH or OR′,

[0072] R″ is hydrogen, alkyl with preferably 1-4 carbon atoms or arylwith preferably 6-12 carbon atoms,

[0073] a is 0, 1, 2 or 3,

[0074] b is 0, 1 or 2,

[0075] a+b together are 1, 2 or 3,

[0076] c is 0, 1 or 2,

[0077] d is 0, 1 or 2,

[0078] c+d together are 2,

[0079] m is preferably 1, but can also be 2, 3, 4 or possibly an evenhigher number, but only when m is no greater than 1, when a+b means 1 or2,

[0080] n is preferably 1, but can also be 2, 3, 4 or possibly an evenhigher number,

[0081] o is 0 or 1, and

[0082] p is 0 or 1.

[0083] The polycondensates can be composed exclusively of compounds ofthe Formula X; however they can also form the aforementionedpolycondensate together with further hydrolysed silanes and/or othermetal compounds and/or filling agents and/or adjuvants. Thepolycondensates are obtained through hydrolysis and condensation of thesilane compounds of the Formula X, if necessary in the presence offurther substances that are to be embedded, e.g. condensation catalysts,as we know them from the state of the art.

[0084] The inventive silicic acid polycondensates can be used in avariety of applications. Here we would only like to mention coatingmasses, binding agents for ceramic particles, adhesives or castingcompounds by way of example. The presence of phosphorous-containingradicals in the polycondensates or coatings or compounds as mentionedabove offers the products properties not known until now. Apart from theaforementioned improvement of flame resistance, the following should bementioned: Since the phosphorous-containing radical is a charge carrier,the behavior of the polycondensates in dispersions or emulsions ismodified. This can be beneficial when they are used in electrophoreticenamelling processes. The compounds produced this way exhibit a modifiedconducting behavior and different anti-static behavior. Products shouldexhibit improved corrosion protection behavior. The solubility ofcompounds of the Formula I in polar solvents is better so that it ispossible to process them in another spectrum of solvents.

[0085] The following shall explain the invention in more detail based onexamples.

EXAMPLE 1

[0086] Reaction of trimethylolpropane triacrylate with3-mercaptopropylmethyldimethyloxy silane (described in DE-PS 40 11 044and EP 0451709) and subsequently with diethyl phosphite.

[0087] Reaction Process:

[0088] Reaction of a dimethyl acrylate silane with diethyl phosphite andsubsequent hydrolysis and condensation

[0089] (Reaction Process Described with Formulas) Katalysator = catalystAdditionsisomere = addition isomers Hydrolyse = hydrolysis Kondensation= condensation Aufarbeitung = processing

[0090] Under cooling conditions, a dry protective gas atmosphere andstirring, 1.06 g of an ethanolic KOH solution is added dropwise to 4.61g (15.5 mmol) trimethylolpropane triacrylate (TMPTA). Under the sameconditions, 2.80 g (15.5 mmol) 3-mercaptopropylmethyldimethoxy silaneare added dropwise, wherein the temperature in the reaction vessel risesslightly. In about 5 minutes, the SH groups are completed converted (canbe proven with the iodine test), and the reaction (thiol addition) hasbeen completed. The resulting clear reaction mixture is first mixed with2.13 g diethyl phosphite (15.5 mmol) under the aforementioned conditionsand subsequently with a 25% sodium methanolate solution as the catalyst.The course of the reaction and thus the complete conversion of thisexothermic PH addition can be proven by means of IR spectroscopy basedon the following changes:

[0091] disappearance of the V_(PH) bands at 2431 cm⁻¹

[0092] decrease of the V_(CH) bands (olefin) at 3040 cm⁻¹

[0093] decrease of the v_(C=C) bands at 1635/1619 cm¹

[0094] The resulting phosphonate-modified acrylate silane (isomermixture) can also be isolated in the form of a viscous liquid throughusual processing or preferably directly reacted further.

EXAMPLE 2

[0095] Reaction of glycerine-1,3-dimethacrylate with 3-isocyanate propyltriethoxy silane (described in DE-PS 40 11 044 and EP 0451709) andsubsequently with diethyl phosphite

[0096] Reaction Process:

[0097] Reaction of a diacrylate silane with diethyl phosphite andsubsequent hydrolysis and condensation

[0098] (Reaction Process Described with Formulas) Katalysator = catalystAdditionsisomere = addition isomers Hydrolyse = hydrolysis Kondensation= condensation Aufarbeitung = processing

[0099] Under a dry atmosphere and stirring, 18.55 g (75.0 mmol) of3-isocyanate propyl triethoxy silane are added dropwise to 17.12 g (75.0mmol) glycerine-1,3-dimethacrylate and dibutyl tin dilaurate as additioncatalyst. The course of the reaction (addition of the NCO group of thesilane to the OH group of the methacrylate) is tracked by means of IR.Upon complete reaction, first 10.31 diethyl phosphite (75.0 mmol) areadded at room temperature under a dry protective gas atmosphere andstirring, and subsequently a 25% sodium methanolate solution is addeddropwise as the catalyst. The course of the reaction and thus thecomplete conversion of this exothermic PH addition can be proven bymeans of IR spectroscopy based on the following changes:

[0100] disappearance of the V_(PH) bands at 2431 cm⁻¹

[0101] decrease of the V_(CH) bands (olefin) at 3040 cm⁻¹

[0102] decrease of the v_(C=C) bands at 1638 cm⁻¹

[0103] The resulting phosphonate-modified methacrylate silane (isomermixture) can also be isolated in form of a viscous liquid through theusual processing or preferably directly reacted further.

EXAMPLE 3

[0104] Hydrolysis and condensation of the compound obtained in Example 2

[0105] For the hydrolysis and condensation of the above-mentionedreaction mixture about 75 ml acetic ester as well as aqueous HCl areadded. The course of hydrolysis (e.g. Si(OC₂H₅)₃ and PO(OC₂H₆)₂ istracked through the consumption of water by means of H₂O titration. Uponcomplete hydrolysis of the ethoxy groups, the resulting solution shouldbe suitable e.g. for coating (with subsequent curing, i.e.polymerization of the methacrylate groups) any substrates.

1. Compounds of the Formula I(X_(a)R_(b)Si)_(m)[—{B}—([O]_(c)P[O]_(p)R′_(c)Y_(d))_(n)]_(4-a-b)  Iwherein the groups, radicals and indices have the following meanings: Bis at least a doubly-divalent, straight-chained or branched group withat least one organic polymerisable radical and at least 3 carbon atoms,X is a radical that can be cleaved from the silicon atom by hydrolysis,R is possibly substituted alkyl, alkenyl, aryl, alkylaryl or arylalkyl,R′ has the same meaning as R, Y is Cl, OH or OR′, R″ is hydrogen, alkylor aryl, a is 0, 1, 2or 3, b is 0, 1 or 2, a+b together are 1, 2 or 3, cis 0, 1 or 2, d is 0, 1 or 2, c+d together are 2, m is at least 1, withthe specification that m is not greater than 1, when a+b means 1 or 2, nis at least 1, o is 0 or 1, and p is 0 or
 1. 2. Compounds of the FormulaI pursuant to claim 1, wherein X is hydrogen, halogen, hydroxy, alkoxy,acyloxy, alkylcarbonyl, alkoxycarbonyl or NR″ and can possibly havedifferent meanings in a compound of the Formula I, and R″ is alkyl with1-4 carbon atoms or aryl with 6-12 carbon atoms.
 3. Compounds of theFormula I pursuant to claim 1 or 2, wherein B contains at least onenorbornen, acrylate or methacrylate group.
 4. Compounds of the Formula Ipursuant to one of the previous claims, wherein the index o is zero. 5.Compounds of the Formula I pursuant to one of the claims 1 through 3,wherein the index o is equal to
 1. 6. Compounds of the Formula Ipursuant to claim 5, wherein the index p is 1 and the index c is zero.7. Silicic acid polycondensate, obtained through the hydrolyticcondensation of at least one compound of the Formula X(X_(a)R_(b)Si)_(m)[—{B}—([O]₀P[O]_(p)R′_(c)Y_(d))_(n)]_(4-a-b)  X,wherein the groups, radicals and indices have the following meanings: B⁷is at least one doubly-divalent, straight-chained or branched group withat least 1 carbon atom, X is a radical that can be cleaved from thesilicon atom by hydrolysis, R is possibly substituted alkyl, alkenyl,aryl, alkylaryl or arylalkyl, R′ has the same meaning as R, Y is Cl, OHor OR′, R″ is hydrogen, alkyl, a is 0, 1, 2 or 3, b is 0, 1 or 2, a+btogether are 1, 2 or 3, c is 0, 1 or 2, d is 0, 1 or 2, c+d together are2, m is at least 1, with the specification that m can only be 1 when a+bmeans 1 or 2, n is preferably 1, o is 0 or 1, and p is 0 or 1, andpossibly further hydrolysable and condensable silanes and/or furtherhydrolytically condensable compounds of elements from the group of B,Al, P, Sn, Pb, the transition metals, the lanthanides and the actinides,possibly in mixture with further constituents, with the specificationthat a silicic acid polycondensate of trialkyoxysilyl-ethane- or propanephosphoric acid diethyl ester or 1,3-bis[diethylphosphonoethyl]tetra-ethyl disiloxane in combination with a polymerdispersion of a water-insoluble organo-polymer is excluded.
 8. Silicicacid polycondensate pursuant to claim 7, characterized in that in thecompound of the Formula X the group B⁷ contains one or more organicpolymerisable radical, the substituent X is hydrogen, halogen, hydroxy,alkoxy, acyloxy, alkylcarbonyl, alkoxycarbonyl or NR″ and possibly canhave different meanings and the substituent R″ is alkyl with 1-4 carbonatoms or aryl with 6-12 carbon atoms.
 9. Silicic acid polycondensatepursuant to claim 7 or 8, characterized in that in the compound ofFormula X the group B⁷ contains at least one norbornen, acrylate ormethacrylate group.
 10. Method for producing compounds of the Formula Ias defined in claim 4, characterized by the reaction of a compound ofthe Formula II (X_(a)R_(b)Si)_(m)[—{B¹}]_(4-a-b)  II, wherein theradicals and indices X, R, a, b and m have the meanings as defined inFormula I pursuant to claim 1 and B¹ is a derivative of the group B asdefined in Formula I of claim 1 with one additional organicpolymerisable group and has a valency that is lower by 1, with acompound of the Formula III H—P[O]_(p)R′_(c)Y_(d)  III, wherein theradicals and indices R′, Y, c and d have the meanings provided inFormula I of claim 1 and p is
 1. 11. Method for producing a compoundwith Formula I as defined in claim 6, characterized in that a compoundof the Formula IV (X_(a)R_(b)Si)_(m)[—{B}]_(4-a-b)  IV, wherein theradicals and indices X, R, a, b and m have the meanings as defined inFormula I of claim 1 and B² is a derivative of the group B as defined inFormula I of claim 1 with one additional OH group and a valency that islower by 1, is reacted in the presence of an alkaline catalyst withPOCl₃, subsequently the developed HCl is cleaved, groups Y with themeaning Cl are converted possibly by alkoholysis or hydrolysis intogroups with the meaning OH or OR′ and subsequently the obtained compoundis cleaned of by-products with the Formula I.
 12. Method for producing acompound of Formula I as defined in claim 6, wherein the radical Y is OHand the index d means 2, characterized in that a compound of the FormulaIV (X_(a)R_(b)Si)_(m)[—{B²}]_(4-a-b)  IV, wherein the radicals andindices X, R, a, b and m have the meanings as defined in Formula I ofclaim 1 and B² is a derivative of the group B as defined in Formula I ofclaim 1 with one additional OH group and a valency that is lower by 1,is reacted with P₂O₅.
 13. Method for producing a compound of Formula Ias defined in claim 4, characterized by the reaction of a compound ofthe Formula V (X_(a)R_(b)Si)_(m)[—{B³}]_(4-a-b)  V, wherein the group B³is a derivative of the group B as defined in Formula I of claim 1 withone additional halogen atom and a valency that is lower by 1, with aphosphorous compounds of the formula VI, R′_(c)PY_(d)  VI wherein R′ andY have the meanings provided for Formula I in claim 1 and c is 0, 1 or2, d is 1, 2 or 3 and c+d is 3.